US9358537B1 - Styrene based ion exchange resins with oxine functionalized groups - Google Patents

Styrene based ion exchange resins with oxine functionalized groups Download PDF

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US9358537B1
US9358537B1 US14/027,552 US201314027552A US9358537B1 US 9358537 B1 US9358537 B1 US 9358537B1 US 201314027552 A US201314027552 A US 201314027552A US 9358537 B1 US9358537 B1 US 9358537B1
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Prior art keywords
ion exchange
oxine
styrene based
iron
resin
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US14/027,552
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Paul J. Miranda
Corby G. Anderson
Edward Rosenberg
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Montana Technological University
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Montana Tech of the University of Montana
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J41/00—Anion exchange; Use of material as anion exchangers; Treatment of material for improving the anion exchange properties
    • B01J41/08—Use of material as anion exchangers; Treatment of material for improving the anion exchange properties
    • B01J41/12—Macromolecular compounds
    • B01J41/14—Macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J39/00—Cation exchange; Use of material as cation exchangers; Treatment of material for improving the cation exchange properties
    • B01J39/08—Use of material as cation exchangers; Treatment of material for improving the cation exchange properties
    • B01J39/16—Organic material
    • B01J39/18—Macromolecular compounds
    • B01J39/19—Macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon-to-carbon bonds
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
    • C22B3/42—Treatment or purification of solutions, e.g. obtained by leaching by ion-exchange extraction
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
    • B01D15/08—Selective adsorption, e.g. chromatography
    • B01D15/26—Selective adsorption, e.g. chromatography characterised by the separation mechanism
    • B01D15/36—Selective adsorption, e.g. chromatography characterised by the separation mechanism involving ionic interaction, e.g. ion-exchange, ion-pair, ion-suppression or ion-exclusion
    • B01D15/361—Ion-exchange

Definitions

  • the invention involves the selective removal of certain metals from aqueous systems using a selective ligand ion exchange resin.
  • iron, as ferric, or gallium is selectively removed from other metals, such as copper, cobalt, and nickel, in acidic solutions by a styrene resin with oxine functionalized groups.
  • the resin is stripped to concentrate the either ferric iron or gallium from the initial solution for further treatment.
  • the stripped resin can be used again over many cycles for further selective removal of iron or gallium from solution.
  • the invention can be easily applied to contaminated streams, process streams, acid rock drainages, or other potential iron or gallium containing solutions.
  • FIG. 1 is a diagram of a preferred embodiment of an oxine ligand styrene based ion exchange resin of the subject invention.
  • FIG. 2 is a graph showing the selective removal of Fe from an aqueous solution by a preferred embodiment of the resin of the subject invention.
  • FIG. 3 is a graph showing the removed Fe being stripped from the preferred embodiment of the resin in FIG. 2 .
  • the invention involves a styrene based ion exchange resin with oxine functionalized groups that selectively remove certain metals from mixed metal solutions.
  • the subject resin can be used to remove other metals, including but not limited to, copper, cobalt, rhodium, zinc, cerium, lanthanum, germanium, nickel, platinum, palladium, uranium, antimony, cadmium, indium and molybdenum, from mixed metal solutions.
  • Oxine based ligands are used in solvent extraction techniques to remove metals from mine leach solutions. These oxine ligand solvent extraction techniques however suffer from the deficiencies of other solvent extraction techniques.
  • the subject method provides an effective and efficient means to remove unwanted metals from an aqueous solution.
  • Oxine base ligands are functionally chemically attached to a styrene base to provide a selective ligand ion exchange resin.
  • FIG. 1 A preferred embodiment of the subject resin is shown in FIG. 1 and can be prepared by the following method:

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Geology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
  • Manufacture And Refinement Of Metals (AREA)
  • Removal Of Specific Substances (AREA)

Abstract

Oxine ligands placed on styrene base ion exchange resins selectively remove iron and gallium from acidic solutions. After loading, the oxine resin is stripped of the loaded metals and used again for further metal removal. The resins can be used for process streams, acid rock drainages, or any other iron or gallium containing solution.

Description

CROSS-REFERENCE TO RELATED APPLICATIONS
This application is a continuation of co-pending U.S. patent application Ser. No. 12/693,367, filed Jan. 25, 2010, which claims the benefits of U.S. Provisional Application No. 61/147,025, filed Jan. 23, 2009, the disclosure of which is hereby incorporated by reference in its entirety including all figures, tables and drawings.
STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH OR DEVELOPMENT
This invention was made with Government support under Grant No. CR-19476 A 429231 awarded by the Center for Advanced Separation Technologies. The Government has certain rights in the invention.
REFERENCE TO SEQUENCE LISTING, A TABLE, OR A COMPUTER PROGRAM LISTING COMPACT DISC APPENDIX
Not applicable
BACKGROUND OF THE INVENTION
Many mining companies utilize acid based leaching techniques for copper and other potential metals. During this process, unwanted metals, such as iron, leach into solution, therefore, further processing must be employed for iron removal or selective separation of valuable metals. These techniques include solvent extraction, precipitation, and/or ion exchange methods.
Current technologies used for ferric iron removal, such as precipitation techniques, produce large amounts of iron containing sludge and require large amounts of chemicals. For solvent extraction techniques, the raffinate, a liquid steam that remains after the extraction with the immiscible liquid to remove solutes from the original liquor, can easily become contaminated with iron and lower overall removal efficiency. Other ion exchange resins from removal of iron from solutions have been successfully created, however, these technologies utilize phosphonate ligands and have low overall capacities.
BRIEF SUMMARY OF THE INVENTION
The invention involves the selective removal of certain metals from aqueous systems using a selective ligand ion exchange resin. In a particularly preferred embodiment, iron, as ferric, or gallium is selectively removed from other metals, such as copper, cobalt, and nickel, in acidic solutions by a styrene resin with oxine functionalized groups. After metal loading of the resin, the resin is stripped to concentrate the either ferric iron or gallium from the initial solution for further treatment. The stripped resin can be used again over many cycles for further selective removal of iron or gallium from solution. The invention can be easily applied to contaminated streams, process streams, acid rock drainages, or other potential iron or gallium containing solutions.
BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWING
FIG. 1 is a diagram of a preferred embodiment of an oxine ligand styrene based ion exchange resin of the subject invention.
FIG. 2 is a graph showing the selective removal of Fe from an aqueous solution by a preferred embodiment of the resin of the subject invention.
FIG. 3 is a graph showing the removed Fe being stripped from the preferred embodiment of the resin in FIG. 2.
 DETAILED DESCRIPTION OF THE INVENTION
The invention involves a styrene based ion exchange resin with oxine functionalized groups that selectively remove certain metals from mixed metal solutions.
Although iron and gallium have the highest affinity for the functionalized oxine ligands of the ion exchange resin of the subject invention, the subject resin can be used to remove other metals, including but not limited to, copper, cobalt, rhodium, zinc, cerium, lanthanum, germanium, nickel, platinum, palladium, uranium, antimony, cadmium, indium and molybdenum, from mixed metal solutions. Oxine based ligands are used in solvent extraction techniques to remove metals from mine leach solutions. These oxine ligand solvent extraction techniques however suffer from the deficiencies of other solvent extraction techniques. The subject method provides an effective and efficient means to remove unwanted metals from an aqueous solution. Oxine base ligands are functionally chemically attached to a styrene base to provide a selective ligand ion exchange resin.
A preferred embodiment of the subject resin is shown in FIG. 1 and can be prepared by the following method:
  • 1) A styrene based amine ligand ion exchange (IX) resin is used (either primary amine or secondary amine).
  • 2) For initial reaction, each gram of IX resin is reacted and mixed with 1 milliliter of formaldehyde and 0.1 milliliter acetic acid for 24 hours.
  • 3) The solid liquid mixture is then filtered with the IX resin remaining.
  • 4) The IX resin is then reacted with 4 times the amount of methanol in milliliters and dissolved 8-hydroxyquinoline (1×) adjusted to pH=9 with ammonium hydroxide.
  • 5) The solid liquid mixture is refluxed at 70 degrees centigrade for 24 hours.
  • 6) The solid liquid mixture is filtered off and the reacted ion exchange resin is rinsed with dilute ammonium hydroxide, then distilled water, then dilute acetic acid, and distilled water.
Laboratory column testing has been completed on solutions containing iron, manganese, and zinc for selective iron removal. Flow rate for testing was done at 0.20 bed volumes per minute and samples taken every bed volume. (FIG. 2) After testing, the sample was successfully stripped with sulfuric acid and analyzed for iron, manganese, and zinc (FIG. 3).
It is understood that the foregoing examples are merely illustrative of the present invention. Certain modifications of the articles and/or methods may be made and still achieve the objectives of the invention. Such modifications are contemplated as within the scope of the claimed invention.

Claims (3)

The invention claimed is:
1. A method making a selective ligand ion exchange resin comprising the steps of:
providing a styrene based amine ligand ion exchange resin, the amine containing group connected to the styrene based ion exchange resin by a first linking organic group; and
executing the Mannich reaction to attach an 8-hydroxyquinoline ligand to said styrene based amine ion exchange resin through a second linking organic group.
2. The method of claim 1, wherein said amine containing group is a primary amine.
3. The method of claim 1, wherein said amine containing group is a secondary amine.
US14/027,552 2009-01-23 2013-09-16 Styrene based ion exchange resins with oxine functionalized groups Active US9358537B1 (en)

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US14702509P 2009-01-23 2009-01-23
US12/693,367 US8535528B1 (en) 2009-01-23 2010-01-25 Styrene based ion exchange resins with oxine functionalized groups
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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4112044A (en) * 1975-09-06 1978-09-05 Asahi Kasei Kogyo Kabushiki Kaisha Chromatographic separation of uranium isotopes
US4222892A (en) * 1977-07-21 1980-09-16 Japan Atomic Energy Research Institute Process for preparing oxine impregnated-activated charcoal
US4659512A (en) * 1983-12-21 1987-04-21 Pedro B. Macedo Fixation of dissolved metal species with a complexing agent
US4876232A (en) * 1987-09-28 1989-10-24 Pedro B. Macedo Supported heteropolycyclic compounds in the separation and removal of late transition metals
US5069942A (en) * 1990-04-30 1991-12-03 E. I. Du Pont De Nemours And Company Process for improving adhesion of polysiloxane coatings to polymeric substrates via reduced alkali metal cation content
US6758967B1 (en) * 2003-04-28 2004-07-06 Alltech Associates, Inc. Liquid chromatography apparatus having two stationary phases
US8535528B1 (en) * 2009-01-23 2013-09-17 Montana Tech Of The University Of Montana Styrene based ion exchange resins with oxine functionalized groups

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4112044A (en) * 1975-09-06 1978-09-05 Asahi Kasei Kogyo Kabushiki Kaisha Chromatographic separation of uranium isotopes
US4222892A (en) * 1977-07-21 1980-09-16 Japan Atomic Energy Research Institute Process for preparing oxine impregnated-activated charcoal
US4659512A (en) * 1983-12-21 1987-04-21 Pedro B. Macedo Fixation of dissolved metal species with a complexing agent
US4876232A (en) * 1987-09-28 1989-10-24 Pedro B. Macedo Supported heteropolycyclic compounds in the separation and removal of late transition metals
US5069942A (en) * 1990-04-30 1991-12-03 E. I. Du Pont De Nemours And Company Process for improving adhesion of polysiloxane coatings to polymeric substrates via reduced alkali metal cation content
US6758967B1 (en) * 2003-04-28 2004-07-06 Alltech Associates, Inc. Liquid chromatography apparatus having two stationary phases
US8535528B1 (en) * 2009-01-23 2013-09-17 Montana Tech Of The University Of Montana Styrene based ion exchange resins with oxine functionalized groups

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